9.2.

40
AOAC Official Method 993.14
Trace Elements in Waters and Wastewaters
Inductively Coupled PlasmaMass Spectrometric Method

(h) Centrifuge.Steel cabinet with guard bowl, electric timer,

and brake, capable of 2000 g.
(i) Drying oven.Gravity convection oven with thermostatic
control capable of maintaining 105 5.

First Action 1993

(Applicable to determination of 20 trace elements, at concentrations

of 0.8200 g/L, in finished drinking water, groundwater, and
wastewaters.)
(Caution: The following reagents are highly toxic: antimony, arsenic trioxide, beryllium sulfate, cadmium, chromium trioxide, lead nitrate, selenium dioxide, thallium nitrate,
and uranium nitrate. See Appendix B for safe handling
of special chemical hazards. Consult Material Safety
Data Sheets for information on disposal. See Appendix
B for safe handling of acids.)
Method Performance:
See Table 993.14A for method performance data.
A. Principle

Method describes multielement determination of trace elements

by inductively coupled plasmamass spectrometry (ICPMS). Elements are digested in a nitrichydrochloric acid solution. Sample
material in solution is introduced by pneumatic nebulization into
radiofrequency plasma where energy transfer processes cause desolvation, atomization, and ionization. Ions are extracted from plasma
through differentially pumped vacuum interface and are separated
on the basis of mass-to-charge ratio by a quadrupole mass spectrometer having minimum resolution capability of 1 amu peak width
at 5% peak height. Ions transmitted through quadrupole are detected
by continuous dynode electron multiplier assembly, and ion information is processed by data handling system.
B. Apparatus

(a) Inductively coupled plasmamass spectrometer.(1) Instrument capable of scanning mass range 5250 amu with minimum
resolution capability of 1 amu peak width at 5% peak height and that
may be fitted with conventional or extended dynamic range detection
system. (2) Argon gas supply (high-purity grade, 99.99%). (3)
Variable-speed peristaltic pump required for solution delivery to
nebulizer. (4) Mass-flow controller on nebulizer gas supply may be
required. Water-cooled spray chamber beneficial in reducing interferences. Operating conditions: Because of diversity in instrumentation, manufacturer-provided operating conditions should be
followed.
(b) Glassware.Volumetric flasks, graduated cylinders, funnels, centrifuge tubes, and calibrated pipets.
(c) Beakers.250 mL conical Phillips with 50 mm watch glasses
and 250 mL Griffin with 75 mm watch glasses.
(d) Storage bottles.125 and 250 mL, narrow mouth, Teflon
FEP (fluorinated ethylene propylene), with Tefzel ETFE (ethylene
tetrafluorethylene) screw caps.
(e) Air displacement pipetter.Digital, capable of 102500 L
range and disposable pipet tips.
(f) Analytical balance.Sensitivity 0.1 mg.
(g) Hot plate.With variable temperature, controllable to 3.

C. Reagents

(a) Nitric acid (HNO3) solutions.(1) HNO3.Concentrated,

specific gravity 1.41. (2) HNO3 solution (1 + 1).Add 500 mL
HNO3 to 400 mL reagent water and dilute to 1 L. (3) HNO3 solution
(1 + 9).Add 100 mL HNO3 to 400 mL reagent water and dilute to
1 L. (4) 1% (volume/volume) HNO3 solution. (5) 2% (volume/volume) HNO3 solution.
(b) Hydrochloric acid (HCl) solutions.(1) HCl.Concentrated, specific gravity 1.41. (2) HCl solution (1 + 1).Add 500 mL
HCl to 400 mL reagent water and dilute to 1 L.
(c) Ammonium hydroxide (NH4OH).Concentrated, specific
gravity 0.902.
(d) Tartaric acid.
(e) Reagent water.ASTM type I water (ASTM D1193) is required. Prepare water by distillation, polishing with mixed bed of ion
exchange material, and filtration through 0.2 m membrane filter.
(f) Standard solutions.Purchase or prepare from ultra high-purity chemicals or metals (99.9999.999% pure). Pickle metals
(where indicated), to clean surfaces and reduce mass, by adding
20% excess of metal to acid; dry, weigh, and repeat process until
desired weight is achieved. Dry salts 1 h at 105 , except where noted.
Use reagent water, (e), for all dilutions unless otherwise specified.
Store stock solutions in Teflon bottles, B(d). Accurately weigh all
amounts to nearest 0.1 mg.
(1) Aluminum stock solution (1000 mg Al/mL).Pickle Al
metal in 7580 (1 + 1) HCl solution, (b)(2), to 0.100 g. Dissolve
metal in 10 mL HCl, (b)(1), and 2 mL HNO3, (a)(1), by heating
ca 30 min at 7580. Continue heating until solution has evaporated to 4 mL. Cool to room temperature and add 4 mL reagent
water. Evaporate to 2 mL by heating. Cool to room temperature
and dilute to 100 mL.
(2) Antimony stock solution (1000 g Sb/mL).Dissolve 0.100 g
Sb powder in 2 mL (1 + 1) HNO3 solution, (a)(2), and 0.5 mL HCl.
Heat at 7580 to dissolve, cool to room temperature, and add 20 mL
reagent water and 0.15 g tartaric acid, (d). Warm solution to dissolve
white precipitate. Cool and dilute to 100 mL.
(3) Arsenic stock solution (1000 g As/mL).Dissolve 0.1320 g
As2O3 in mixture of 50 mL reagent water and 1 mL NH4OH, (c), by
heating at 7580; cool to room temperature; and acidify with 2 mL
HNO3. Dilute to 100 mL.
(4) Barium stock solution (1000 g Ba/mL).Dissolve 0.1437 g
BaCO3 in mixture of 10 mL reagent water and 2 mL HNO3 by
heating while stiring. Dilute to 100 mL.
(5) Beryllium stock solution (1000 g Be/mL).Dissolve 1.965 g
BeSO44H2O (DO NOT DRY) in 50 mL reagent water. Add 1 mL
HNO3. Dilute to 100 mL.
(6) Bismuth stock solution (1000 g Bi/mL).Dissolve 0.1115 g
Bi2O3 in 5 mL HNO3 by heating at 7580, cool to room temperature,
and dilute to 100 mL.
(7) Cadmium stock solution (1000 g Cd/mL).Pickle Cd metal
in (1 + 9) HNO3 solution, (a)(3), to 0.100 g. Dissolve in 5 mL (1 +
1) HNO3 solution by heating at 7580, cool to room temperature,
and dilute to 100 mL.

Copyright 1998 AOAC INTERNATIONAL

Table 993.14A Method Performance for Trace Elements in Water, Inductively Coupled Plasma-Mass Spectrometric Method
Spike
Added,
Recovery,
Recovery,
Analyte
%
sR
sr
RSDR, %
RSDr, %
g/L
g/L
Reagent Water
Aluminum

Antimony

Arsenic

Barium

Beryllium

Cadmium

Chromium

Cobalt

Copper

Lead

8.00
12.00
56.00
80.00
160.00
200.00

10.01
10.98
59.13
82.59
158.95
200.89

125.13
91.50
105.59
103.24
99.34
100.45

2.33
5.16
5.55
4.92
11.82
8.61

1.74

2.80
4.00
20.00
28.00
80.00
100.00

2.75
4.22
19.76
27.48
82.52
98.06

98.21
105.50
98.80
98.14
103.15
98.06

0.27
0.46
1.09
1.38
2.24
1.34

0.27

8.00
12.00
56.00
80.00
160.00
200.00

8.64
12.58
55.44
85.15
161.80
201.52

108.00
104.83
99.00
106.44
101.13
100.76

3.01
3.18
4.64
2.54
11.15
10.81

3.02

8.01
12.00
48.00
64.00
160.00
200.00

7.58
11.81
47.32
65.52
157.09
198.53

94.63
98.42
98.58
102.38
98.18
99.27

0.50
1.05
1.60
2.90
6.53
8.28

0.48

2.80
4.00
20.00
28.00
80.00
100.00

3.31
4.45
22.38
30.02
84.18
102.88

118.21
111.25
111.90
107.21
105.23
102.88

0.81
0.73
2.76
2.86
4.79
5.90

0.26

4.00
6.00
20.00
28.00
80.00
100.00

4.01
6.32
19.81
28.33
81.28
100.11

100.25
105.33
99.05
101.18
101.60
100.11

0.34
0.49
1.12
0.94
4.91
3.24

0.20

8.00
12.00
56.00
80.00
160.00
200.00

8.27
13.88
57.86
84.73
157.66
197.43

103.38
115.67
103.32
105.91
98.54
98.72

0.32
3.10
4.03
2.65
13.62
9.47

1.54

0.80
1.21
20.10
28.20
80.50
101.00

0.88
0.98
20.77
27.75
78.59
98.79

110.00
80.99
103.33
98.40
97.63
97.81

0.10
0.04
0.74
0.96
2.29
2.94

0.05

4.00
6.00
20.00
28.00
80.00
100.00

3.88
6.14
20.07
27.97
79.80
99.57

97.00
102.33
100.35
99.89
99.75
99.57

0.73
1.00
1.08
1.94
3.22
4.42

0.59

4.00
6.00
20.00
28.00
80.00
100.00

4.00
5.56
20.54
30.90
80.57
102.93

100.00
92.67
102.70
110.36
100.71
102.93

1.57
2.00
2.91
4.58
3.13
6.62

1.62

4.19
8.90

0.85
1.76

3.51
3.96

1.82
4.07

1.00
4.02

0.86
1.33

2.68
6.97

0.67
2.31

0.92
1.91

4.36
4.29

Copyright 1998 AOAC INTERNATIONAL

23.28
46.99
9.39
5.96
7.44
4.29

16.58

9.82
10.90
5.52
5.02
2.71
1.37

7.75

34.84
25.28
8.37
2.98
6.89
5.36

28.46

6.60
8.89
3.38
4.43
4.16
4.17

4.95

24.47
16.40
12.33
9.53
5.69
5.73

6.70

8.48
7.75
5.65
3.32
6.04
3.24

3.87

3.87
22.33
6.97
3.13
8.64
4.80

13.91

11.36
4.08
3.56
3.46
2.91
2.98

5.38

18.81
16.29
5.38
6.94
4.04
4.44

11.78

39.25
35.97
14.17
14.82
3.88
6.43

33.89

5.91
4.95

3.60
1.95

4.99
2.18

3.23
2.29

3.82
4.30

3.57
1.47

3.76
3.93

2.76
2.60

3.83
2.13

16.95
4.68

Table 993.14A Method Performance for Trace Elements in Water, Inductively Coupled Plasma-Mass Spectrometric Method
(Continued)
Spike
Added,
Recovery,
Recovery,
Analyte
%
sR
sr
RSDR, %
RSDr, %
g/L
g/L
Manganese

Molybdenum

Nickel

Selenium

Silver

Thallium

Thorium

Uranium

Vanadium

Zinc

0.80
1.20
20.00
28.00
80.00
100.00

0.86
1.09
20.43
27.53
79.00
97.60

107.50
90.83
102.15
98.32
98.75
97.60

0.15
0.12
0.89
0.41
3.16
2.51

0.09

2.80
4.00
20.00
28.00
80.00
100.00

2.63
3.85
19.75
27.87
83.07
100.08

93.93
96.25
98.75
99.54
103.84
100.08

0.32
0.31
0.64
1.07
3.07
4.32

0.16

4.00
6.00
20.00
28.00
80.00
100.00

4.02
6.36
19.93
28.02
79.29
100.87

100.50
106.00
99.65
100.07
99.11
100.87

0.41
0.91
1.30
1.25
2.95
7.20

0.50

32.00
40.00
80.00
96.10
160.00
200.00

33.54
41.03
81.40
98.34
165.58
214.30

104.81
102.58
101.75
102.33
102.24
107.15

4.63
6.04
5.86
8.57
15.69
10.57

1.57

0.80
1.20
48.00
64.00
160.00
200.00

0.93
1.51
49.39
63.54
136.42
153.74

116.25
125.83
102.90
99.28
85.26
76.87

0.09
0.23
3.25
2.75
48.31
57.34

0.14

2.80
4.00
20.00
28.00
80.00
100.00

2.89
3.92
19.27
28.08
81.29
96.69

103.21
98.00
96.35
100.29
101.61
96.69

0.23
0.15
0.99
0.83
3.65
2.86

0.22

0.80
1.20
20.00
28.00
80.10
100.00

0.93
1.22
20.88
27.97
81.14
102.64

116.25
101.67
104.40
99.89
101.30
102.64

0.16
0.19
0.90
1.11
2.99
3.39

0.09

0.80
1.20
20.10
28.10
80.30
100.00

0.86
1.10
21.38
28.36
82.47
103.49

107.50
91.67
106.37
100.93
102.70
103.49

0.05
0.11
0.99
1.10
4.03
5.24

0.08

32.00
40.00
80.00
96.00
160.00
200.00

31.02
38.54
79.14
93.47
162.43
208.20

96.94
96.35
98.93
97.36
101.52
104.10

2.68
2.94
4.94
3.85
5.67
2.65

2.19

8.00
12.00
56.00
80.00
160.00
200.00

8.33
15.49
56.07
85.53
165.17
207.27

104.13
129.08
100.13
106.91
103.23
103.64

2.56
4.18
2.91
5.81
7.78
14.61

1.78

0.72
2.38

0.64
1.78

0.63
2.55

5.44
9.86

1.81
12.19

0.67
2.86

0.71
2.14

0.82
2.16

4.29
3.30

2.47
9.87

Copyright 1998 AOAC INTERNATIONAL

17.44
11.01
4.36
1.49
4.00
2.57

9.23

12.17
8.05
3.24
3.84
3.70
4.32

4.94

10.20
14.31
6.52
4.46
3.72
7.14

9.63

13.80
14.72
7.20
8.71
9.59
4.93

4.21

9.68
15.23
6.58
4.33
35.41
37.30

11.48

7.96
3.83
5.14
2.96
4.49
2.96

6.46

17.20
15.57
4.31
3.97
3.68
3.30

8.37

5.81
10.00
4.63
3.88
4.89
5.06

8.16

8.64
7.63
6.24
4.12
3.49
1.27

6.30

30.73
26.99
5.19
6.79
4.71
7.05

14.95

3.00
2.70

2.69
1.94

2.63
2.83

6.05
5.22

3.21
8.40

2.83
3.21

2.91
2.33

3.30
2.32

4.97
1.78

3.49
5.30

Table 993.14A Method Performance for Trace Elements in Water, Inductively Coupled Plasma-Mass Spectrometric Method
(Continued)
Spike
Added,
Recovery,
Recovery,
Analyte
%
sR
sr
RSDR, %
RSDr, %
/L
/L
Drinking Water
Aluminum

Antimony

Arsenic

Barium

Beryllium

Cadmium

Chromium

Cobalt

Copper

Lead

6.34

8.00
12.00
56.00
80.00
160.00
200.00

11.18
11.02
56.97
82.73
159.89
189.98

139.75
91.83
101.73
103.41
99.93
94.99

9.02
3.02
7.14
8.01
11.94
12.97

2.80
4.00
20.00
28.00
80.00
100.00

2.73
4.10
19.17
26.48
83.43
97.19

97.50
102.50
95.85
94.57
104.29
97.19

0.29
0.47
1.37
1.72
2.05
5.31

0.17

8.00
12.00
56.00
80.00
160.00
200.00

9.00
11.37
53.77
87.72
157.56
197.99

112.50
94.75
96.02
109.65
98.48
99.00

3.13
1.77
4.12
4.14
4.83
10.66

1.96

8.01
12.00
48.00
64.00
160.00
200.00

8.21
12.56
49.13
65.30
155.25
196.52

102.50
104.67
102.35
102.03
97.03
98.26

1.21
1.79
3.72
4.16
7.82
5.70

1.11

2.80
4.00
20.00
28.00
80.00
100.00

3.15
4.45
21.27
29.57
87.59
102.64

112.50
111.25
106.35
105.61
109.49
102.64

0.47
0.51
1.23
1.67
6.89
6.27

0.31

4.00
6.00
20.00
28.00
80.00
100.00

4.11
5.87
19.57
27.68
80.62
98.15

102.75
97.83
97.85
98.86
100.78
98.15

0.88
0.58
1.45
1.27
4.45
3.60

0.71

8.00
12.00
56.00
80.00
160.00
200.00

9.46
13.10
56.04
84.38
158.24
196.72

118.25
109.17
100.07
105.48
98.90
98.36

2.34
2.39
2.24
3.18
5.12
7.47

2.08

0.80
1.21
20.10
28.20
80.50
101.00

0.92
1.02
20.45
27.29
78.04
97.62

115.00
84.30
101.74
96.77
96.94
96.65

0.45
0.10
0.91
1.22
3.72
4.62

0.31

4.00
6.00
20.00
28.00
80.00
100.00

3.33
5.95
18.90
27.21
76.64
96.17

83.25
99.17
94.50
97.18
95.80
96.17

0.85
1.78
1.64
2.76
5.30
5.64

0.99

4.00
6.00
20.00
28.00
80.00
100.00

3.44
6.84
20.18
28.08
80.92
101.60

86.00
114.00
100.90
100.29
101.15
101.60

1.15
1.10
1.20
1.57
2.30
3.23

1.18

6.18
10.59

0.66
2.46

4.07
6.30

3.77
5.67

0.63
1.88

1.26
2.02

1.29
3.16

0.53
1.84

1.51
3.42

1.44
2.07

Copyright 1998 AOAC INTERNATIONAL

80.68
27.40
12.53
9.68
7.47
6.83

57.12

10.62
11.46
7.15
6.50
2.46
5.46

4.98

34.78
15.57
7.66
4.72
3.07
5.38

19.24

14.74
14.25
7.57
6.37
5.04
2.90

10.69

14.92
11.46
5.78
5.65
7.87
6.11

8.16

21.41
9.88
7.41
4.59
5.52
3.67

14.23

24.74
18.24
4.00
3.77
3.24
3.80

18.44

48.91
9.80
4.45
4.47
4.77
4.73

31.96

25.53
29.92
8.68
10.14
6.92
5.86

21.34

33.43
16.08
5.95
5.59
2.84
3.18

22.96

8.85
6.05

2.89
2.72

5.75
3.54

6.59
3.22

2.48
1.98

5.33
2.26

1.84
1.78

2.22
2.09

6.55
3.96

5.97
2.27

Table 993.14A Method Performance for Trace Elements in Water, Inductively Coupled Plasma-Mass Spectrometric Method
(Continued)
Spike
Added,
Recovery,
Recovery,
Analyte
%
sR
sr
RSDR, %
RSDr, %
g/L
g/L
Manganese

Molybdenum

Nickel

Selenium

Silver

Thallium

Thorium

Uranium

Vanadium

Zinc

0.80
1.20
20.00
28.00
80.00
100.00

0.96
1.13
21.06
27.60
79.57
97.97

120.00
94.17
105.30
98.57
99.46
97.97

0.32
0.38
1.32
1.47
4.18
4.10

0.42

2.80
4.00
20.00
28.00
80.00
100.00

2.80
3.95
19.78
27.87
85.65
99.06

100.00
98.75
98.90
99.54
107.06
99.06

0.20
0.47
0.60
1.51
3.50
2.89

0.32

4.00
6.00
20.00
28.00
80.00
100.00

3.66
5.44
18.42
27.09
75.84
95.83

91.50
90.67
92.10
96.75
94.80
95.83

0.53
1.32
0.87
1.68
4.40
4.41

1.03

32.00
40.00
80.00
96.10
160.00
200.00

32.57
42.18
79.97
94.94
163.48
212.19

101.78
105.45
99.96
98.79
102.18
106.10

4.37
3.71
6.66
7.90
9.17
16.49

3.65

0.80
1.20
48.00
64.00
160.00
200.00

0.70
1.37
45.43
60.35
119.06
172.15

87.50
114.17
94.65
94.30
74.41
86.08

0.34
0.33
6.78
2.22
55.28
31.92

2.80
4.00
20.00
28.00
80.00
100.00

2.88
3.96
19.77
27.61
85.32
100.07

102.86
99.00
98.85
98.61
106.65
100.07

0.40
0.21
1.13
1.24
4.08
4.33

0.16

0.80
1.20
20.00
28.00
80.10
100.00

0.78
1.09
21.66
28.09
79.99
100.50

97.50
90.83
108.30
100.32
99.86
100.50

0.13
0.19
0.94
0.83
2.03
4.56

0.07

0.80
1.20
20.10
28.10
80.30
100.00

0.85
1.05
22.30
28.89
80.31
100.70

106.25
87.50
110.95
102.81
100.01
100.70

0.15
0.13
1.40
1.47
2.00
5.30

0.09

32.00
40.00
80.00
96.00
160.00
200.00

33.15
40.20
77.83
96.32
161.89
214.91

103.59
100.50
97.29
100.33
101.18
107.46

2.51
1.88
4.18
1.34
7.63
5.89

2.28

8.00
12.00
56.00
80.00
160.00
200.00

11.60
10.21
56.83
82.88
156.69
191.59

145.00
85.08
101.48
103.60
97.93
95.80

6.18
4.96
7.66
8.34
17.01
17.21

5.72

0.96
2.01

1.16
3.07

1.11
3.94

5.28
10.06
0.34
5.15
36.34

0.83
4.05

0.54
2.60

0.46
2.71

2.75
6.56

4.56
9.48

Copyright 1998 AOAC INTERNATIONAL

33.33
33.63
6.27
5.33
5.25
4.18

40.19

7.14
11.90
3.03
5.42
4.09
2.92

9.48

14.48
24.26
4.72
6.20
5.80
4.60

22.64

13.42
8.80
8.33
8.32
5.61
7.77

9.77

48.57
24.09
14.92
3.68
46.43
18.54

32.85

13.89
5.30
5.72
4.49
4.78
4.33

4.68

16.67
17.43
4.34
2.95
2.54
4.54

7.49

17.65
12.38
6.28
5.09
2.49
5.26

9.47

7.57
4.68
5.37
1.39
4.71
2.74

6.22

53.28
48.58
13.48
10.06
10.86
8.98

52.45

3.95
2.26

4.87
3.32

4.88
4.59

6.04
5.36

9.74
24.96

3.50
4.37

2.17
2.88

1.80
2.99

3.16
3.48

6.53
5.44

Table 993.14A Method Performance for Trace Elements in Water, Inductively Coupled Plasma-Mass Spectrometric Method
(Continued)
Spike
Recovery,
Recovery,
Recovery,
Analyte
%
sR
sr
RSDR, %
RSDr, %
g/L
g/L
Groundwater
Aluminum

Antimony

Arsenic

Barium

Beryllium

Cadmium

Chromium

Cobalt

Copper

Lead

2.70

8.00
12.00
56.00
80.00
160.00
200.00

9.86
13.40
51.75
82.83
155.40
189.64

123.25
111.67
92.41
103.54
97.13
94.82

7.10
10.27
10.78
33.37
15.39
31.46

2.80
4.00
20.00
28.00
80.00
100.00

2.82
4.02
20.12
27.77
80.34
101.09

100.71
100.50
100.60
99.18
100.43
101.09

0.19
0.35
0.82
1.38
9.14
2.89

0.22

8.00
12.00
56.00
80.00
160.00
200.00

10.40
7.85
53.25
83.60
159.86
194.41

130.00
65.42
95.09
104.50
99.91
97.21

5.17
4.62
3.49
12.46
11.67
18.24

4.90

8.01
12.00
48.00
64.00
160.00
200.00

8.04
12.85
50.12
69.53
164.44
208.32

100.37
107.08
104.42
108.64
102.78
104.16

2.60
1.45
2.98
2.66
8.81
9.22

2.24

2.80
4.00
20.00
28.00
80.00
100.00

3.02
4.27
21.55
29.24
84.23
103.39

107.86
106.75
107.75
104.43
105.29
103.39

0.46
0.44
1.72
2.09
9.05
10.17

0.22

4.00
6.00
20.00
28.00
80.00
100.00

3.98
5.62
18.15
28.86
77.83
95.31

99.50
93.67
90.75
95.93
97.29
95.31

0.48
0.73
1.73
2.59
3.05
2.04

0.14

8.00
12.00
56.00
80.00
160.00
200.00

8.98
13.42
59.35
83.90
164.58
199.88

112.25
111.83
105.98
104.88
102.86
99.94

1.47
1.13
5.99
5.70
14.11
11.19

0.37

0.80
1.21
20.10
28.20
80.50
101.00

0.85
1.04
20.81
28.07
79.26
99.41

106.25
85.95
103.53
99.54
98.46
98.43

0.13
0.18
1.11
2.16
4.66
4.22

0.09

4.00
6.00
20.00
28.00
80.00
100.00

3.86
5.96
18.97
27.44
79.30
97.54

96.50
99.33
94.85
98.00
99.13
97.54

1.40
0.95
1.68
2.58
9.05
11.16

0.71

4.00
6.00
20.00
28.00
80.00
100.00

4.20
6.27
19.57
28.55
82.47
102.47

105.00
104.50
97.85
101.96
103.09
102.47

1.13
2.38
2.72
1.73
4.38
3.58

1.76

16.92
19.27

0.97
6.80

7.88
14.94

2.19
6.61

1.10
4.32

0.88
1.88

5.42
9.80

1.12
1.34

2.32
6.54

0.88
2.69

Copyright 1998 AOAC INTERNATIONAL

72.01
76.64
20.83
40.29
9.90
16.59

23.22

6.74
8.71
4.08
4.97
11.38
2.86

6.43

49.71
58.85
6.55
14.90
7.30
9.38

53.70

32.34
11.28
5.95
3.83
5.36
4.43

21.45

15.23
10.30
7.98
7.15
10.74
9.84

6.04

12.06
12.99
9.53
9.64
3.92
2.14

2.92

16.37
8.42
10.09
6.79
8.57
5.60

3.30

15.29
17.31
5.33
7.70
5.88
4.25

9.52

36.27
15.94
8.86
9.40
11.41
11.44

14.46

26.90
37.96
13.90
6.06
5.31
3.49

33.62

25.14
11.17

4.05
7.50

11.52
8.43

3.66
3.55

4.33
4.61

3.91
2.17

7.57
5.38

4.58
1.50

10.00
7.40

3.66
2.91

Table 993.14A Method Performance for Trace Elements in Water, Inductively Coupled Plasma-Mass Spectrometric Method
(Continued)
Spike
Recovery,
Recovery,
Recovery,
Analyte
%
sR
sr
RSDR, %
RSDr, %
/L
/L
Manganese

Molybdenum

Nickel

Selenium

Silver

Thallium

Thorium

Uranium

Vanadium

Zinc

0.80
1.20
20.00
28.00
80.00
100.00

0.64
0.90
19.61
25.65
77.38
95.86

80.00
75.00
98.05
91.61
96.73
95.86

0.22
0.21
2.60
4.10
6.13
6.74

0.17

2.80
4.00
20.00
28.00
80.00
100.00

3.00
3.60
20.69
28.80
84.26
103.57

107.14
90.00
103.45
102.86
105.33
103.57

0.47
0.90
1.37
2.01
4.13
6.10

0.42

4.00
6.00
20.00
28.00
80.00
100.00

4.81
6.67
20.58
30.73
82.71
101.00

120.25
111.17
102.90
109.75
103.39
101.00

2.06
3.66
3.71
3.75
9.49
9.89

2.82

32.00
40.00
80.00
96.10
160.00
200.00

32.46
41.46
81.63
98.92
167.54
209.21

101.44
103.65
102.04
102.93
104.71
104.61

4.95
3.30
6.94
4.39
8.69
14.65

3.24

0.80
1.20
48.00
64.00
160.00
200.00

0.70
0.98
45.59
59.71
121.43
160.69

87.50
81.67
94.98
93.30
75.89
80.35

0.26
0.28
4.27
6.58
42.55
27.15

2.80
4.00
20.00
28.00
80.00
100.00

2.88
3.88
20.22
28.65
83.97
101.09

102.86
97.00
101.10
102.32
104.96
101.09

0.14
0.37
1.05
1.50
6.10
4.15

0.12

0.80
1.20
20.00
28.00
80.10
100.00

0.87
1.15
21.78
29.86
86.00
107.35

108.75
95.83
108.90
106.64
107.37
107.35

0.17
0.17
0.90
1.65
3.43
4.72

0.07

0.80
1.20
20.10
28.10
80.30
100.00

0.84
1.10
21.56
29.86
85.01
106.47

105.00
91.67
107.26
106.26
105.87
106.47

0.23
0.14
1.11
1.83
3.76
3.74

0.19

32.00
40.00
80.00
96.00
160.00
200.00

33.25
40.34
84.42
98.70
170.94
217.90

103.91
100.85
105.53
102.81
106.84
108.95

3.83
3.08
3.97
5.03
9.09
11.36

1.87

8.00
12.00
56.00
80.00
160.00
200.00

7.29
12.66
54.86
78.62
150.12
184.37

91.13
105.50
97.96
98.28
93.83
92.19

1.12
3.24
5.12
8.56
12.52
16.59

2.62
2.90

1.11
4.81

2.37
5.42

5.65
12.98
0.10
2.70
28.19

0.65
6.05

0.94
1.95

1.08
2.00

2.93
11.55
2.20
7.24
10.84

Copyright 1998 AOAC INTERNATIONAL

34.38
23.33
13.26
15.98
7.92
7.03

22.08

15.67
25.00
6.62
6.98
4.90
5.89

12.73

42.83
54.87
18.03
12.20
11.47
9.79

49.13

15.25
7.96
8.50
4.44
5.19
7.00

8.77

37.14
28.57
9.37
11.02
35.04
16.90

11.90

4.86
9.54
5.19
5.24
7.26
4.11

3.55

19.54
14.78
4.13
5.53
3.99
4.40

6.93

27.38
12.73
5.15
6.13
4.42
3.51

19.59

11.52
7.64
4.70
5.10
5.32
5.21

5.08

15.36
25.59
9.33
10.89
8.34
9.00

22.06

11.58
3.35

4.49
5.12

9.24
5.90

6.26
6.89

5.13
19.98

2.66
6.54

3.64
2.02

4.20
2.09

3.20
5.94

10.85
6.48

(8) Chromium stock solution (1000 g Cr/mL).Dissolve 0.1923

g CrO3 in mixture of 10 mL reagent water and 1 mL HNO3. Dilute
to 100 mL.
(9) Cobalt stock solution (1000 g Co/mL).Pickle Co metal in
(1 + 9) HNO3 solution to 0.100 g. Dissolve in 5 mL (1 + 1) HNO3
solution by heating at 7580, cool to room temperature, and dilute
to 100 mL.
(10) Copper stock solution (1000 g Cu/mL).Pickle Cu metal
in (1 + 9) HNO3 solution to 0.100 g. Dissolve in 5 mL (1 + 1) HNO3
solution by heating at 7580, cool to room temperature, and dilute
to 100 mL.
(11) Indium stock solution (1000 g In/mL).Pickle In metal in
(1 + 1) HNO3 solution to 0.100 g. Dissolve in 10 mL (1 + 1) HNO3
solution by heating at 7580 , cool to room temperature, and dilute
to 100 mL.
(12) Lead stock solution (1000 g Pb/mL).Dissolve 0.1599 g
PbNO3 in 5 mL (1 + 1) HNO3 solution. Dilute to 100 mL.
(13) Magnesium stock solution (1000 g Mg/mL).Dissolve
0.1658 g MgO in 10 mL (1 + 1) HNO3 solution by heating at 7580,
cool to room temperature, and dilute to 100 mL.
(14) Manganese stock solution (1000 g Mn/mL).Pickle Mn
flake in (1 + 9) HNO3 solution to 0.100 g. Dissolve in 5 mL (1 + 1)
HNO3 solution by heating at 7580, cool to room temperature, and
dilute to 100 mL.
(15) Molybdenum stock solution (1000 g Mo/mL).Dissolve
0.1500 g MoO3 in mixture of 10 mL reagent water and 1 mL
NH4OH by heating at 7580, cool to room temperature, and dilute
to 100 mL.
(16) Nickel stock solution (1000 g Ni/mL).Dissolve 0.100 g Ni
powder in 5 mL HNO3 by heating at 7580, cool to room temperature, and dilute to 100 mL.
(17) Scandium stock solution (1000 g Sc/mL).Dissolve
0.1534 g Sc 2O 3 in 5 mL (1 + 1) HNO 3 solution by heating at
7580 , cool to room temperature, and dilute to 100 mL.
(18) Selenium stock solution (1000 g Se/mL).Dissolve 0.1405
g SeO2 in 20 mL reagent water. Dilute to 100 mL.
(19) Silver stock solution (1000 g Ag/mL).Dissolve 0.100
g Ag metal in 5 mL (1 + 1) HNO3 solution by heating at 7580
, cool to room temperature, and dilute to 100 mL. Store in amber
container.
(20) Terbium stock solution (1000 g Tb/mL).Dissolve 0.1176
g Tb4O7 in 5 mL HNO3 by heating at 7580, cool to room temperature, and dilute to 100 mL.
(21) Thallium stock solution (1000 g Tl/mL).Dissolve 0.1303
g TlNO3 in mixture of 10 mL reagent water and 1 mL HNO3. Dilute
to 100 mL.
(22) Thorium stock solution (1000 g Th/mL).Dissolve 0.2380
g Th(NO3)44H2O (DO NOT DRY) in 20 mL reagent water. Dilute
to 100 mL.
(23) Uranium stock solution (1000 g U/mL).Dissolve 0.2110
g UO2(NO3)2 6H2O (DO NOT DRY) in 20 mL reagent water. Dilute
to 100 mL.
(24) Vanadium stock solution (1000 g V/mL).Pickle V metal
in (1 + 9) HNO3 solution to 0.100 g. Dissolve in 5 mL (1 + 1) HNO3
solution by heating at 7580, cool to room temperature, and dilute
to 100 mL.

(25) Yttrium stock solution (1000 g Y/mL).Dissolve 0.1270 g

Y2O3 in 5 mL (1 + 1) HNO3 solution by heating at 7580, cool to
room temperature, and dilute to 100 mL.
(26) Zinc stock solution (1000 g Zn/mL).Pickle Zn metal in (1
+ 9) HNO3 solution to 0.100 g. Dissolve in 5 mL (1 + 1) HNO3
solution by heating at 7580, cool to room temperature, and dilute
to 100 mL.
(g) Calibration standard solutions (10 g/mL).(1) Standard
solution A.Combine 1 mL each (f)(1), (2), (3), (5), (7), (8), (9),
(10), (12), (14), (15), (16), (18), (21), (22), (23), (24), and (26)
and dilute mixture to 100 mL with 1% (volume/volume) HNO3,
(a)(4).
(2) Standard solution B.Combine 1 mL each (f)(4) and (19) and dilute
to 100 mL with reagent water with 1% (volume/volume) HNO3, (a)(4).
(h) Internal standard solution (100 g/mL).Combine 10 mL
(f)(6), (11), (17), (20), and (25) and dilute to 100 mL with reagent
water, (e). If internal standards are added by peristaltic pump, dilute
using 1% (volume/volume) HNO3, (a)(4). Store in Teflon bottle.
(i) Blanks.(1) Calibration blank.1% (volume/volume)
HNO3, (a)(4), in reagent water, (e). (2) Laboratory reagent blank
(LRB).Containing reagents in same volumes used in processing
samples. (3) Rinse blank.2% (volume/volume) HNO3, (a)(5), in
reagent water, (e).
(j) Tuning solution (100 g/L).Combine 10 mL of (f)(5), (9),
(11), (12), and (13) and dilute to 100 mL with 1% (volume/volume)
HNO3, (a)(4). Internal standards are not added to this solution.
(k) Quality control sample (QCS) (100 g/L).Prepare as directed by diluting USEPA (U.S. Environmental Protection Agency),
Certified Quality Control Sample (SPEX Industries is suitable
source), or equivalent, in reagent water.
(l) Laboratory fortified blank (LFB).Combine portions from
multielement stock standard solutions A, (g)(1), and B, (g)(2), to
reagent water, (e), diluting 1:100 to produce final concentration 100
g/L for each analyte. LFB must be carried through entire sample
digestion and preparation scheme. Add internal standards to LFB if
direct addition procedure is used.
D. Sample Collection and Preservation

For total dissolved elements, filter sample through 0.45 m membrane filter. Acidify filtrate with (1 + 1) HNO3 solution, C(a)(2), to
pH < 2 at time of collection.
For total recoverable elements, acidify sample with (1 + 1) HNO3
solution to pH < 2 at time of collection.
Hold samples ca 16 h prior to analysis.
E. Sample Preparation

For dissolved elements, add 1 mL HNO3, C(a)(1), to 100 mL

filtered, acid-preserved sample.
For total recoverable elements, transfer 100 mL well-mixed,
acid-preserved sample containing 0.25% (weight/volume) total
solids to 250 mL Griffin beaker. Add 1 mL HNO3 and 0.5 mL HCl,
C(b)(1). Heat on hot plate without boiling until volume is reduced
to 1520 mL. Reflux 30 min (very slight boiling may occur). Cool
and transfer to 50 mL volumetric flask or 50 mL class A stoppered
graduated cylinder. Dilute to volume with reagent water, C(e), and
mix. Let insoluble material separate. Pipet 20 mL into 50 mL
volumetric flask, dilute to volume with reagent water, and mix well.
Analyze as soon as possible because effects of various matrices on
diluted sample stability cannot be characterized. Dilute original

Copyright 1998 AOAC INTERNATIONAL

Table 993.14B Recommended Masses and Elemental Equations for

Data Calculations
Element

Elemental Equationa

Mass
b

Aluminum
Antimony
Arsenicc
Barium
Beryllium
Cadmiumd
Chromiume
Cobalt
Copper
Leadf
Manganese
Molybdenumg
Nickel
Seleniumh
Silver
Thallium
Thorium
Uranium
Vanadiumi
Zinc
Krypton
Palladium
Ruthenium
Tin

27
121b , 123
75b
135, 137b
9b
106, 108, 111b, 114
52b, 53
59b
63b, 65
206b, 207b, 208b
55b
95, 97, 98b
60b, 62
77, 82b
107b, 109
203, 205b
232b
238b
51b
66b, 67, 68
83b
105b
99b
118b

Scandiumj
Yttriumk
Indiuml
Terbium
Bismuthk

45b
89b
115b
159b
209b

(1.000)(27C)
(1.000)(121C)
(1.000)(75
C) (3.127)[(77C) (0.815)(82C)]
(1.000)(137
C)
(1.000)(9C)
111
(1.000)(52 C) (1.073)[(108C) (0.712)(106C)]
(1.000)( C)
(1.000)(59
C)
(1.000)(63C)
206
(1.000)(55 C) + (1.000)(207C) + (1.000)(208C)
(1.000)( C)
(1.000)(98
C) (0.146)(99C)
(1.000)(60
C)
(1.000)(82
C)
107
(1.000)(205C)
(1.000)(232C)
(1.000)( C)
(1.000)(238C)
(1.000)(51
C) (3.127){(53C) (0.113)(52C)}
(1.000)(66
C)
(1.000)(83
C)
105
(1.000)(99 C)
(1.000)(118C)
(1.000)( C)

Recommended Internal Standards

(1.000)(45
C)
(1.000)(89C)
115
(1.000)(159C) (0.016)(118C)
(1.000)( C)
(1.000)(209C)

C = calibration blank subtracted counts at specified mass.

Isotopes recommended for analytical determination.
Correction for chloride interference with adjustment for 77Se. ArCl 75/77 ratio may be determined from reagent blank.
d
Correction for MoO interference. Additional isobaric elemental correction should be made if palladium is present.
e
In 0.4% volume/volume HCl background from ClOH will normally be small. However, contribution may be estimated from reagent blank.
f
Allowance for isotopic variability of lead isotopes.
g
Isobaric elemental correction for ruthenium.
h
Some argon supplies contain krypton as impurity. Selenium is corrected for 82Kr by background subtraction.
i
Correction for chloride interference with adjustment for 53Cr. ClO 51/53 ratio may be determined from reagent blank.
j
Polyatomic ion interference.
k
May be present in environmental samples.
l
Isobaric elemental correction for tin.
b
c

sample to contain <100 g/L Ag and digest if analyses indicate Ag

concentration in sample is >100 g/L.
F. Calibration

Initiate proper operating configuration of instrument and data

system. Conduct mass calibration and resolution checks using tuning
solution, C(j). Resolution at low mass is indicated by Mg isotopes
24, 25, and 26; resolution at high mass is indicated by Pb isotopes
206, 207, and 208. Adjust spectrometer resolution to produce 0.75
amu peak width at 5% peak height. Adjust mass calibration if any
Mg or Pb isotope mass is shifted by more than 0.1 amu from unit
mass. Analyze tuning solution 5 times to demonstrate instrument
stability (relative standard deviations should be <5%). Calibrate
instrument for analytes using calibration blank, C(i)(1), and calibration standard solutions A, C(g)(1), and B, C(g)(2), prepared at one
or more concentration levels. See Table 993.14B for recommended
masses and elemental equations for data calculations. Report data as
average of 3 replicate integrations. See Table 993.14C for common
molecular ion interferences. Flush system between solution changes
using rinse blank, C(i)(3).
Internal standardization.For full mass range scans, 3 internal
standards are required. For general application, use 5 internal stan-

dards: Sc, Y, In, Tb, and Bi. Internal standards must be present in
samples, standards, and blanks (200 g/L is recommended).
Instrument performance.After calibration, analyze QCS, C(k).
If measurements exceed 10% QCS limits, terminate analysis, identify and correct source of problem, recalibrate instrument, and
reverify calibration before continuing analyses. To verify instrument
calibration on continuing basis, run calibration blank and calibration
standard as surrogate samples after every 10 analyses. If indicated
concentration deviates from true concentration by >10%, recalibrate
instrument and reanalyze last 10 samples.
G. Quality Control

Minimum quality control requirements for this method include:

(1) initial demonstration of method performance; (2) monitoring of
internal standard area counts in each sample (area of internal standard within 60125% area in calibration blank); (3) analysis of 1
LRB, C(i)(2), with each set of samples as continuing check on
sample contamination; (4) analysis of QCS, C(k), with each set of
samples as continuing check on method recovery; and (5) analysis
of calibration standards, C(g), every 10 analyses as continuing check
on calibration curve (measured values should not exceed 10%
concentration).

Copyright 1998 AOAC INTERNATIONAL

Demonstrate initial, and continuing, method performance every 6

months by digesting 7 spiked reagent water samples at 25 estimated detection limit to determine method detection limits (MDL).
Calculate MDL and compare to results in Table 993.14C.

Table 993.14C Common Molecular Ion Interferences in ICPMS

Molecular Ion
Background molecular ions
CO2H+
ArC+, ArO+
ArN+
ArNH+
40 36 +
Ar Ar
40 38 +
Ar Ar
40
Ar2+
Matrix molecular ions
Chloride
35
ClO+
35
ClOH+
37
ClO+
37
ClOH+
Ar35Cl+
Ar37Cl+
Sulfate
34
SO+
34
SOH+
SO2+, S2+
Phosphate
PO2+
Group I, II Metals
ArNa+
Matrix oxidesb
TiO
ZrO
MoO

Mass

Element Interferencea

45
52
54
55
76
78
80

Sc
Cr
Cr
Mn
Se
Se

51
51
53
54
75
77

V
Cr
Cr
Cr
As
Se

50
51
64

V, Cr
V
Zn

63

Cu

63

Cu

6266
106112
108116

Ni, Cu, Zn
Ag, Cd
Cd

Method elements or internal standards affected by molecular ions.

Oxide interferences will normally be very small and will only impact method
elements when present at relatively high concentrations. Some examples of
matrix oxides are listed.
b

MDL = t S
where t = Students t value for 99% confidence level with n1
degrees of freedom (t = 3.14 for 7 replicates) and S = standard
deviation of the 7 replicate analyses.
Demonstrate continuing check on method recovery by digesting
and analyzing 1 QCS with each set of samples and compare recovery
to performance-based acceptance limits presented in Table 993.14D.
If indicated concentration of any analyte deviates from acceptance
limits, reanalyze QCS for that analyte. Recalibrate for all analytes
still outside acceptance limits.
Reference: J. AOAC Int. 77, 1004(1994).

Copyright 1998 AOAC INTERNATIONAL

Table 993.14D Total Recoverable Method Detection Limits and Acceptance Limits for QC Check Sample
Method Performancea

Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Lead
Manganese
Molybdenum
Nickel
Selenium
Silver
Thallium
Thorium
Uranium
Vanadium
Zinc

MDLb,
g/L

QC Check Sample
Concentration
g/L

Average Recovery
g/L

sR, %

Acceptance Limits
g/Lc

1.0
0.4
1.4
0.8
0.3
0.5
0.9
0.09
0.5
0.6
0.1
0.3
0.5
7.9
0.1
0.3
0.1
0.1
2.5
1.8

100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100

100.4
99.9
101.6
99.7
105.9
100.8
102.3
97.7
100.3
104.0
98.3
101.0
100.1
103.5
101.1
98.5
101.4
102.6
100.3
105.1

8.20
1.91
5.89
4.20
7.65
4.3
7.23
2.80
4.35
8.09
2.67
3.45
5.42
8.52
5.36
3.54
3.78
4.94
3.79
6.91

76125
94106
84119
87112 d
77123
28814
81117
89106
87113
80128
90106
91110
84116
79128 e
85117
88109
90113
88117
89112
84126

Method performance characteristics calculated using regression equations from collaborative study.
Method detection limit.
Acceptance limits calculated as average recovery 3 standard deviations.
d
Acceptance limits centered at 100% recovery.
e
Statistics estimated from summary statistics at 48 and 64 g/L.
b
c

Copyright 1998 AOAC INTERNATIONAL